New vat dyestuffs of the anthraquinone series



1\To Drawing. Application filed-February 27,,1931, Serial No. 518,910, and inHGe rman-y February 28, 1986;-

Patented May 10, 1932 ROBERT IBERLINER, or LEvERKUsEmoN-rnn-Rnmn GERMANY, 'ASSIGNOR roi Gm Enter. ANILINE woaxarifc; or 'msw' vonx, 1\f.'Y., A CORPORATION or DELAWARE NEW VAT m ssenger Fran nzqrnanoumomrszmrns are obtainable by" reacting upon an anthraquinone acridoneof the probable formula wherein the ws mean halogen -one'y means hydrogen and the other halogen; with alphaaminoanthraquinone in the presence of a/high suitable acid binding agent sodiumac'etat'e magnesium oxide; for example) and ofa copper catalyst, such as copper powder, cop-. per acetate, copperchloride; cuprou's'bromide etc; Reaction takes placewhile heating the reaction mixture and the reaction products separate as soon as they have been'formed.

The sameproducts are obtainable by condensing in a similar manner as-described above alpha-chloroanthraquinone or alphabromoanthraquinone with a compoundof the a probable formula-:

wherein the ms mean halogen atoms, one

3/ stands forhydrogen.

the amino group.

The productsthus obtainable which i V beiconsidered as intermediate produotsimthe and the other yafor manufacture "of my new vatdyestufls cor-- respond to the probable formula o= III I" =0; I

boilingorganio solvent, suchas nitrobenzenef' wherein thems stand for halogen atbmis and naphthalene, etc. and in the 'presence of a in which the group connected with nucleus. H is linked to nucleus I l1'1"5 or 8-positi0n,. and form dark powders diflicultv lysoluble in the usual organic solvents.

These intermediate products are trans-j" formed into especially valuable vat dyestuffs V by subjecting same at elevatedtemperature to the action of suitable ring closing agents, i

such as aluminium chloride, aluminium chloride/pyridine,v aluminium chloride/sodium.

cliloride,etcrc The newvat dyestuffs thus obtainableprob-I ably correspondto the general formulazw j wherein the ws mean halogen atoms and the nucleus II is linked to the nucleus marked I in 5 (NH) -6-position or in 8 (NH) -7-positi on.- They form olive colored powdersnearsoluble in strong sulfuric acid with a violet coloration and dye cotton from an, alkaline hydrosulfite vat strong olive shades of excellent'fastnessproperties. I

The following examples illustrate my invention without, however, limiting it there chloroanthraquinone with 1 molof the potassium salt of anthranilic acid, heating the reaction; product with strong sulfuric acid,

--distributing the 8 chloroanthraquinone-acri- V done thus obtainable in 'nitrobenzene 'or another suitable organic solvent,adding a trace of iodine, and leading a current of chlorine through themixture at a temperature of about @-;-100 C.) and 50 parts by weight of 1- aminoanthraquinone are heated to boiling for several hours with 5 0'parts by weightof sodium acetate, 10 parts by Weight of mag-- nesium oxide, 2 parts by weight of copper 'powder and 2 parts by weight of cupric chlo- 3O ride in 1000 parts by weight of naphthalene: The reaction product separates in form of small fine, bluish grey needles. When the reaction is complete toluene" is added, and after filtering the reaction product is boiled with dilute hydrochloric acid. It dissolves in concentrated sulfuric acid with a reddish brown coloration and on pouring into water yields corinth colored flakes.

5 parts by weight of the'condensation product thus produced are heated to 120-130 C with 20 parts by Weight of aluminium chloride in 50 parts by weightof pyridine for a short time'until a worked up test --portion dissolves in concentrated sulfuric acid with a violet coloration. The melt is then stirred'into a solution of 50 parts by weight of sodium hydroxide in 400 parts by V 7 weight of Water. parts by weight of :cchlorine Water are added and the pyridine .50 is then driven off with steam. The resulting product'is an olive colored powder, which dissolves in sulfuric acid with a violet coloration. Cotton is dyed from a'yellowish brown i 5'5? fvat very strongly in" yellowish olive shades of very good fastness.

Example parts by weight ofhthe condensation product from 4.5-Bz-2l4rrtetrachloroanthraquinone-1.2-acridone (obtain- ,6.. .ableby chloronating 5-chloroanthraquinone- 1.2-acridone in nitrobenzene solution as described for the starting material of Example 1 and two molecules of l-ainino-anthraquinone are converted intoa carbazole compound as described in Example 1 by means of 20 parts by weight of aluminium chloride in H g g I reddish olive shades'thanthe product of Elily insoluble, in the "usual-organic solvents,

pyridine or in a mixture of 'aluminiu'rnchlo ride and sodium chloride. The product obtained dyes cotton from a brown vat in more ample 1 and possesses the same satisfactory fastness properties. I claim:+. 1. The new vat general formulae I V wherein the .zps mean'halogen atoms and the nucleus, marked II is linked to the nucleus yestufls of the probable V V i 75 ored powders, nearly insoluble in the usual organic solvents, soluble in'strong sulfuric acid with a violet coloration and dyeing cotton from an alkaline hydrosulfite vat strong formula: V V

olive shadesof excellent fastness properties, 2. The new vat dyestuff of theprobable der, nearly j insoluble in the usual organic solvents,solu ble in stron'gsulfuric'acid with i s yellowish brown vat strong olive shades of excellent fastness properties.

3. The new vat dyestufi' of the probable formula 

